We report on a new approach to the fabrication of an electronic material: organic–inorganic pHEMA–oxo-TiO₂ hybrid with efficient light-induced separation of charges. Particular attention is paid to the material nanoscale morphology. The size-selected 5.0 nm titanium oxo-alkoxy nanoparticles are prepared in a sol–gel reactor with rapid (turbulent) fluid micromixing and the ligand exchange results in a stable nanoparticulate precursor in HEMA solution, in which polymerization can be induced thermally or by photons. The obtained hybrid materials demonstrate the highest quantum yield of photoinduced charge separation of 50% and can store photoinduced electrons at a number density above 10% Ti atoms.